High adsorption to methylene blue based on Fe3O4–N-banana-peel biomass charcoal

This research focused on utilizing banana peel as the primary material for producing mesoporous biomass charcoal through one-step potassium hydroxide activation. Subsequently, the biomass charcoal underwent high-temperature calcination with varying impregnation ratios of KOH : BC for different durations in tubular furnaces set at different temperatures. The resultant biomass charcoal was then subjected to hydrothermal treatment with FeCl3·6H2O to produce biochar/iron oxide composites. The adsorption capabilities of these composites towards methylene blue (MB) were examined under various conditions, including pH (ranging from 3 to 12), temperature variations, and initial MB concentrations (ranging from 50 to 400 mg L−1). The adsorption behavior aligned with the Langmuir model and demonstrated quasi-secondary kinetics. After five adsorption cycles, the capacity decreased from 618.64 mg g−1 to 497.18 mg g−1, indicating considerable stability. Notably, Fe3O4–N-BC exhibited exceptional MB adsorption performance.


Introduction
According to statistics, more than 10 000 commercial dye products are introduced into the aquatic environment.The textile industry is a primary contributor to water pollution, alongside signicant sectors such as paint, leather, paper, and printing industries. 1,2Methylene blue (MB) stands as a representative cationic organic dye, commonly utilized in various industries such as papermaking, silk, cotton, wool, and hair coloring.With the economy experiencing rapid growth, industrial production processes are yielding increasingly large volumes of dye effluent, predominantly composed of organic compounds like azo, amino, and phenyl compounds.The discharge of wastewater containing dyes not only pollutes the aquatic environment but also disrupts the ecological balance of aquatic life and poses risks to human health. 3Elevated levels of MB in water can lead to noticeable changes in color and turbidity, along with potential skin irritation and neurological effects.Prolonged consumption of water contaminated with dyes poses a severe risk to human health, causing signicant damage to the liver and digestive system over time. 4Therefore, it is imperative to implement appropriate measures to remove MB from dye wastewater, ensuring both water quality preservation and the safeguarding of human health from contamination.Reports indicate the frequent utilization of various methods for remediating dyes in contaminated wastewater, including Fenton oxidation, 5 photocatalytic oxidation, 6 membrane separation, 7 adsorption, 8 and electrochemical approaches. 9Compared to other approaches, the adsorption method has advantages.It is one of the most extensively used wastewater treatment technologies due to its simple design, high regeneration potential, diverse material source, good performance, and cost-effectiveness. 10ctivated carbon (AC) is a widely utilized adsorbent in wastewater treatment technology owing to its expansive specic surface area, well-suited pore distribution, and robust mechanical and thermal stability. 11However, most AC on the market today is made from coal, lignite, and coking coal as precursors.These resources have the disadvantage of being costly and non-renewable. 12Compared to coal, a non-renewable resource for carbon production, biomass carbon sources are both renewable and widely available.The utilization of biomass energy can reduce dependence on fossil fuels, thereby mitigating air and water pollution.Due to its larger pore structure and more active sites, biomass carbon exhibits enhanced adsorption capacity, which has garnered signicant attention from researchers.Research has demonstrated that BC effectively eliminates hazardous cationic dyes from wastewater. 13rop straws, forestry and agricultural wastes, coal, and municipal sewage can all be used to make BC. 14It can accomplish the recycling and reuse of waste resources in addition to lowering the pollution that rubbish burning and decomposition contribute to the environment.To obtain greater adsorption effects, biomass charcoal's chemical and physical characteristics must be enhanced.The original biomass charcoal's adsorption capacity to remove contaminants from wastewater is still restricted.The primary objective of modication in biomass charcoal is to enhance its specic surface area and pore structure, while concurrently enriching the material's surface functional groups.Additionally, it is crucial for biomass charcoal to facilitate easy separation into solid and liquid components.The recent surge in popularity of iron modication of biomass charcoal is attributed to its ability to introduce magnetic components, thereby facilitating efficient solid-liquid separation. 15Furthermore, adding iron to biomass charcoal can increase its surface area and create a pore structure, resulting in more active sites for adsorption. 16Nevertheless, the application of iron oxide onto biomass charcoal may potentially occupy adsorption sites or impede the pore structure, consequently diminishing its adsorption capacity. 17Nitrogen doping is a promising modifying technique.9][20] Nitrogen-modied biomass charcoal has been frequently employed in catalysis because of its local unpaired electrons. 21It has also been discovered that nitrogen alteration can diminish the surface area and pore volume of biomass charcoal. 22Consequently, the advantages of enhanced surface area, functional groups, and magnetic components are obtained by iron-nitrogen co-doping.The adsorption mechanisms of iron-nitrogen co-modied biomass charcoal for the removal of pollutants may involve pp stacking, surface complexation, hydrogen bonding, and pore diffusion. 23Numerous studies have explored Fe-N modied biomass charcoal as an adsorbent.For instance, Zhou et al. pioneered the development of urea-functionalized magnetic biomass charcoal, employing it as an adsorbent for the extraction of Pb. 24 Ai et al. produced NH 4 Cl-induced magnetic buckwheat husk powder biomass charcoal and utilized it to adsorb tetracycline and Zn(II). 25According to the literature, practically all adsorbent modication materials based on biomass charcoal are carbonized before being activated with an activator.This approach is not only energy-intensive, but it is also complex and time-consuming, and the adsorbed biomass charcoal is difficult to recover. 26Some adsorbents have low adsorption capacity due to their small specic surface area; some adsorbents have problems such as difficulty in separation and recovery; magnetic modication is an excellent solution to their separation and recovery; however, magnetic modication generally leads to a decrease in the adsorbent's adsorption capacity, so novel adsorption materials must be developed to maintain a magnetic adsorbent while also having a high adsorption capability.FeCl 3 can be used as a magnetic source to improve the separation and recovery capacity of biochar due to its low cost and low pollution.
In this study, biomass charcoal was prepared with banana peels as precursors and potassium hydroxide as an activator.To investigate the impact of temperature, activator ratio, and carbonization period on adsorption performance, an orthogonal experiment was created.To make nitrogen-modied biomass charcoal (N-BC), nd the ideal preparation conditions, combine it with urea in these settings, and pyrolyze.To manufacture magnetic Fe 3 O 4 , utilize a hot solvent approach.Then, dope Fe 3 O 4 with biomass charcoal to create Fe 3 O 4 -N-BC, which is very valuable, recyclable, and makes the adsorbent magnetic to lower secondary recycling costs.The iron-nitrogen co-modication method presents several advantages, including the augmentation of surface area, enhancement of functional groups, and introduction of magnetic components, potentially rendering it a feasible alternative for biochar preparation.To explore the impacts of Fe and N modication on the morphology, chemical composition, and functional groups of biomass charcoal, the sample underwent characterization using scanning electron microscopy (SEM), X-ray diffraction (XRD), Xray photoelectron spectroscopy (XPS), and vibrating-sample magnetometry (VSM).

Preparation of adsorbent
Preparation of modied biomass charcoal.The banana peels underwent a series of preparatory steps: they were initially washed with deionized water, dried, and then ground through a 40-mesh sieve using a grinder.Subsequently, 2.5 g of banana peel powder was mixed with varying proportions of KOH, followed by the addition of a specic quantity of urea.The mixture was then combined with deionized water, dried in an oven at 105 °C for 24 hours, and subsequently transferred into a tube furnace.The sample was subjected to a heating rate of 5 °C min −1 under a nitrogen atmosphere of 400 mL min −1 , reaching a nal temperature of 700 °C with an isothermal hold of 90 minutes.Following cooling, residual KOH was removed by washing the samples with HCl, followed by several rinses with deionized water until a neutral pH was attained.The resulting product was then dried in an oven at 80 °C for 24 hours to yield nitrogen-modied biomass charcoal (N-BC).
Because of the intricate interplay among reaction conditions, pinpointing suitable synthesis parameters proves challenging through single reaction conditions alone.Hence, an orthogonal design method was employed to elucidate the impact of each individual response factor. 27,28The orthogonal design table is shown in the Table S1 (ESI), † which mainly discusses the effects of biomass precursor type, carbonization time, carbonization temperature, and activator dosage on synthesis.
Preparation of Fe 3 O 4 -modied biomass charcoal.A total of 16.32 g of NaAc$3H 2 O and 6.54 g of FeCl 3 $6H 2 O were added to 70 mL of ethylene glycol solution and subjected to magnetic stirring until completely dissolved.The resulting solution was then poured into a 100 mL reaction kettle and heated to 180 °C for 12 h.Aer the reaction is completed, it is washed with deionized water and absolute ethanol in sequence, and then vacuum dried at 60 °C to obtain Fe 3 O 4 .Then, 0.5 g of the prepared Fe 3 O 4 and 0.3 g of the biomass charcoal prepared in the optimal group of the orthogonal experiment were uniformly dispersed into 70 mL of deionized water using ultrasound, and then the Fe 3 O 4 and N-BC mixture was poured into a 100 mL reactor and reacted at 180 °C for 4 hours.The synthesized material was subjected to magnetic separation aer cooling, followed by rinsing with anhydrous ethanol and deionized water, and subsequent vacuum drying at 60 °C to yield the iron oxide and nitrogen co-doped biochar (Fe 3 O 4 -N-BC).The synthesis diagram of Fe 3 O 4 -N-BC is shown in Fig. 1.
Adsorption experiment.Firstly, methylene blue standard solution (1000 mg L −1 ) was prepared with deionized water, and all methylene blue solutions were prepared according to this standard solution.HCl and NaOH of 0.1 mol L −1 were prepared to adjust pH.In this experiment, the concentration of dye solution was determined by ultraviolet spectrophotometer at the maximum absorption wavelength l = 664 nm (Fig. S1, ESI †).In this research, three adsorption tests were conducted on each experimental sample and the average value was taken.
Adsorption kinetics.5 mg adsorbent was mixed in methylene blue solution of 25 mL 300 mg L −1 , and adsorption experiments were carried out at 25 °C and pH natural conditions at different times.Then the dynamic model is used to t the data.
Adsorption isotherm.Dispersed 5 mg of adsorbent in 25 mL MB solutions of different concentrations, adsorb under natural pH conditions of 25 °C, 35 °C, and 45 °C, conduct isotherm research, and then used the isotherm model to t the relevant data.
Adsorption thermodynamics.A methylene blue solution, initially concentrated at 300 mg L −1 , was chosen.Successive 25 mL dye solutions were introduced to 5 mg adsorbents under ambient pH conditions.The adsorbents underwent adsorption at temperatures of 25, 35, and 45 °C.Upon reaching adsorption equilibrium, the remaining dye solution concentration was measured, followed by thermodynamic tting.
The impact of pH on adsorption performance.0.1 M HCl and 0.1 M NaOH were employed to modulate the pH of the dye solution within the pH range of 3-12 at 25 °C.Subsequently, 10 mg of adsorbent was dispersed in 25 mL of a 300 mg L −1 MB solution at various pH levels.Post-adsorption equilibrium, the concentration of the MB solution was ascertained.
Incorporate a specied quantity of Fe 3 O 4 -N-BC adsorbent into 25 mL of dye solutions with varying concentrations.Following adsorption at a consistent temperature for a duration, the supernatant is magnetically isolated and subjected to measurement using a UV spectrophotometer at the wavelength of maximum absorption, l = 664 nm.According to the standard curve generated for the methylene blue dye (Fig. S2, ESI †).Measure the absorbance of the dye.The adsorption capacity q e (mg g −1 ) (eqn ( 1)) and removal rate R (%) (eqn (2)) under different conditions are calculated by the following formulas: where C 0 (mg L −1 ) and C e (mg L −1 ) are the initial concentration of the dye solution and the concentration aer the dye adsorption reaches equilibrium, V (mL) is the initial volume of the dye solution, and m (g) is the amount of adsorbent.

Characterization
The sample's morphology was analyzed using scanning electron microscopy (SEM) coupled with an energy dispersive spectrometer (EDS).Aer the biomass charcoal was dissolved in concentrated hydrochloric acid, the content of biomass charcoal-coated iron was determined by inductively coupled plasma mass spectrometry (ICP-MS).The absorbance of residual dye in water is measured with a UV-visible spectrophotometer (UV).An X-ray diffractometer was employed to capture the inorganic crystal morphology of the sample within the range of 10°to 70°.Raman spectra were acquired utilizing a high-resolution Raman spectrophotometer from HoribaJobin-Yvon.X-ray photoelectron spectroscopy (XPS) spectra were acquired utilizing an ESCALAB250 instrument.The magnetic properties of the samples were assessed at room temperature employing a vibrating sample magnetometer (VSM, Lake-Shore7404).BET specic surface area measurements were performed on a Micromeritics ASAP2020 instrument (ASAP2020, Micromeritis).

Modied synthesis results and characterizations
Results of orthogonal experiment.The results of orthogonal experiments are depicted in Fig. 2. Here, 'i' represents the factors (i = A, B, C), while 'j' indicates the levels (j = 1, 2, 3).In detail, k ij signies the cumulative removal rate at level j for factor i, with the mean value of k ij represented as k ij .R i denotes the range between the maximum and minimum k ij values across the three levels examined.The orthogonal experiments are shown in Table S2.† It can be seen from the gure that the four factors affecting the experimental conditions, carbonization temperature, holding time, biomass type and activator ratio, have an impact on the preparation of biomass charcoal: carbonization temperature > activator ratio > holding time.It can be seen that the carbonization temperature is the most important determining factor.Of course, the proportion of activators is also important.The proportion of activators added ultimately also depends on the carbonization temperature.It will affect the structure of the prepared biomass charcoal, and appropriate holding time can prevent the waste of energy and resources.The optimal levels for each factor are A 2 , B 2 , and C 2 , indicating a carbonization temperature of 700 °C, a holding time of 90 minutes, and a mass ratio of biomass to activator KOH at 1 : 2. For KOH activation, 29 rst KOH interacts with carbon components and is converted into K 2 CO 3 (eqn (3)), then K 2 CO 3 is decomposed into K 2 O and CO 2 (eqn (4)), and the intermediate product further reacts with carbon to form CO (eqn ( 5)-( 7)), the gases (H 2 O, CO 2 , CO, etc.) produced by the reaction help to form a porous structure.The biomass chars utilized in subsequent characterization and adsorption experiments were synthesized at their optimal levels.
Characterization.The morphological characteristics of the biomass charcoal material were studied by obtaining SEM images.Fig. 3 shows the SEM images of different adsorbents BC, N-BC, and Fe 3 O 4 -N-BC.Observations from Fig. 3 (a-f   superparamagnetic at room temperature. 32The magnetic property facilitates the efficient separation of the dye-adsorbed composite material from water.Hence, Fe 3 O 4 -N-BC can serve as a magnetic adsorbent for the removal of pollutants from aqueous solutions. The porous structure of magnetic biomass charcoal composites was characterized using N 2 adsorption/desorption isotherms.The adsorption isotherm of the biochar exhibited a typical type-I prole, characterized by a sharp increase in adsorption at P/P 0 < 0.2, followed by saturation at relatively low relative pressures.4][35] As shown in Fig. 6(b), according to the pore size distribution, its pore structure is mainly distributed in the range of 2-4 nm, conrming the mesoporous structure of biomass charcoal.The specic surface areas of the prepared BC, N-BC, and Fe 3 O 4 -N-BC are shown in Table S3.† Among them, BC has the largest specic surface area of 1827.9321m 2 g −1 , 3.8 times that of Fe 3 O 4 -N-BC.This indicates that KOH activation signicantly enhances the specic surface area of the carbon material.In contrast to BC, nitrogen modication resulted in a decrease in the surface area and total volume of biomass char, while increasing its average pore size.Nitrogen modication appears to hinder the enhancement of biochar surface area and pore structure, a phenomenon inuenced by the choice of modifying reagent (urea) and pyrolysis temperature.Additionally, some studies have suggested that nitrogen modication could potentially reduce the surface area and pore volume of biochar.Consequently, employing the iron-nitrogen co-modication technique could be deemed a favorable option for biochar production owing to its capability to introduce a substantial surface area.The decrease in biochar's specic surface area following nitrogen modication may be ascribed to (1) the narrowing of pores amidst carbon bers within the biochar, (2) the reduction/annealing process leading to the low desorption degree of biochar, 36 (3) the modication results in highly disordered and folded structures. 22The introduction of Fe 3 O 4 leads to a smaller mass proportion of biomass charcoal in the composite material, resulting in a smaller specic surface area.Iron enters the mesoporous carbon, thereby reducing the shrinkage of the matrix carbon during carbonization. 37But compared to other magnetic biomass charcoal, its specic surface area is still larger.KOH, urea and FeCl 3 $6H 2 O react with banana peels, and the gases generated by thermal decomposition during the reaction can improve their structural characteristics and adsorption properties.
The XPS spectrum of biomass charcoal is shown in Fig. 7. C 1s and O 1s can be detected on the surface of biomass charcoal, while Fe 2p can also be detected on   724.3 eV respectively (Fig. 7(d)).711.2 and 724.3 eV are the characteristic peaks of Fe 2p 3/2 and Fe 2p 1/2 , respectively, and the peak at 715.7 eV is basically consistent with the Fe(III) state. 39,42This shows that there are two oxidation states of iron.Combined with XRD analysis, the Fe 2+ and Fe 3+ compounds in biomass charcoal are magnetite (Fe 3 O 4 ) and maghemite (g-Fe 2 O 3 ). 43ffects of different adsorbents on the adsorption of methylene blue.Conduct adsorption tests on methylene blue with the prepared BC, N-BC and Fe 3 O 4 -N-BC, respectively.Take 5 mg of BC, N-BC and Fe 3 O 4 -N-BC respectively and dissolve them in 25 mL of MB solution with an initial concentration of 300 mg L −1 .The pH naturally, the temperature is 298 K.The adsorption capacity is shown in Fig. 8(a).The adsorption capacity of biomass charcoal activated by potassium hydroxide can reach 693.11 mg g −1 , and the adsorption capacity of nitrogen-modied biomass charcoal can reach up to 807.87 mg g −1 .The latter will cause some pores to collapse.Although the load of Fe 3 O 4 will cause the specic surface area to decrease, the adsorption capacity is as high as 640.77mg g −1 .The loading of Fe 3 O 4 results in a slight reduction in adsorption capacity, but gives it magnetism and can be recycled more conveniently.Therefore, it is valuable to sacrice a small amount of adsorption capacity in exchange for its rapid separation capability.Later experiments were conducted on Fe 3 O 4 -N-BC.
Effects of pH.The pH level of the dye solution stands as a pivotal factor, wielding signicant inuence over the adsorption efficacy of the adsorbent.Beyond merely shaping the surface structure and charge of the biomass charcoal, its ionization level within the solution profoundly impacts the cohesion between the adsorbent and the dye molecules, thus inuencing their stability.With this in mind, an investigation into the impact of pH on the removal of MB by biomass charcoal was undertaken.In the pH range of 3.0-12.0,Fe 3 O 4 -N-BC can effectively remove MB.As shown in Fig. 8(b), when the pH rises from 3 to 12, the adsorption behavior of magnetic biomass charcoal to MB rst increases rapidly, then slows down, and nally remains basically unchanged.The adsorption capacity of MB at pH 3 is 306.7 mg g −1 , to 750.8 mg g −1 at pH 12.The reason may be that the abundant H + in the solution competes with the cationic MB for adsorption on the same active site on the adsorbent surface at an initial low pH. 44As the pH increases, the electrostatic adsorption of MB by the adsorbent increases, thereby improving its adsorption effect.
Adsorption kinetics.Adsorbents ensconced within porous materials oen exhibit intricate kinetics, wherein the adsorption pace can be intricately inuenced by a multitude of factors.These include the nature of the adsorbent itself, the surface uniformity or heterogeneity thereof, alongside the pH and temperature of the solution.Furthermore, the presence of characteristic functional groups plays a pivotal role in dictating the adsorption performance.In order to further determine the adsorption performance of N-BC and Fe 3 O 4 -N-BC materials on MB molecules under natural conditions, adsorption equilibrium and kinetic studies were conducted under the conditions of a natural pH value of deionized water solution and temperature of 298 K.The effect of contact time on the adsorption of MB by Fe 3 O 4 -N-BC is shown in Fig. 9(a).It can be seen that the adsorption amount increases rapidly 100 minutes before adsorption, and the adsorption capacity reached 531.17 mg g −1 at 60 min, and slowly increased aer 200 min to nally reach adsorption equilibrium.The surface of Fe 3 O 4 -N-BC has abundant active sites and a high concentration gradient, so the adsorption speed is fast in the initial stage.When the active site surface of Fe 3 O 4 -N-BC is gradually occupied by MB, the repulsive interfacial force between the solid and liquid gradually increases, and the adsorption rate gradually decreases.In order to study the adsorption kinetics and adsorption mechanism process, three typical kinetic models 45 (pseudo-rst-order   kinetics (eqn ( 8))), pseudo-second-order kinetics (eqn ( 9)) and intra-particle diffusion model (eqn (10)) where q e (mg g −1 ) is the equilibrium adsorption capacity, q t (mg g −1 ) is the MB adsorption capacity at time t, k 1 (min −1 ), k 2 (g mg −1 min −1 ) and k p (mg g −1 min −1/2 ) are the adsorption rate constant of pseudo-rst-order kinetics, the adsorption constant of pseudo-second-order kinetics and the intra-particle diffusion rate constant.Fig. 9(a) illustrates the application of nonlinear regression analysis to the dataset employing dynamic equations.The adsorption dataset underwent tting utilizing pseudo-rstorder kinetics, pseudo-second-order kinetics, and intraparticle diffusion models.Detailed parameters are delineated in Table S4.† Notably, Table S4 † reveals that the R 2 values for the pseudo-rst-order and pseudo-second-order kinetics pertaining to methylene blue adsorption by Fe 3 O 4 -N-BC stand at 0.8316 and 0.9929, respectively.Moreover, the maximum adsorption capacities are observed to be 618.15mg g −1 and 656.08 mg g −1 correspondingly.The adsorption of methylene blue by Fe 3 O 4 -N-BC is more consistent with the pseudo-second-order kinetic model, which indicates that the adsorption of MB on this adsorbent is chemical adsorption. 46As can be seen from Fig. 9(b), there are three straight lines tting the intra-particle diffusion to the adsorption of MB on Fe 3 O 4 -N-BC.The initial stage entails the diffusion of MB from the solution to the outer surface of Fe 3 O 4 -N-BC.Subsequently, the second stage encompasses particle diffusion, wherein MB permeates from the outer surface of Fe 3 O 4 -N-BC into the inner pores.Finally, the third stage denotes the equilibrium phase.It is noteworthy that none of these three linear progressions intersects the origin, denoting C s 0, thereby suggesting that particle diffusion alone does not exclusively govern the rate-limiting step. 47dsorption isotherms.11)), 48 Temkin (eqn (12)), 49 and Freundlich (eqn (13)) 50 models were used to conduct isotherm tting studies.
where C e (mg L −1 ) is the dye liquor concentration at equilibrium, q max (mg g −1 ) is the maximum adsorption capacity, In comparison to biochar investigated in prior studies, the maximum adsorption capacity of Fe 3 O 4 -N-BC for MB, as displayed in Table 1, remains notably elevated.This observation underscores the effectiveness of Fe and N modication, signifying its promising potential for practical application.
Adsorption thermodynamics analysis.In order to explore the effect of temperature on adsorption, thermodynamic analysis was performed.As can be seen from Fig. 10(b), as the adsorption temperature increases from 298 K to 318 K, the adsorption amount of MB gradually increases.In order to further study the relationship, the thermodynamic formula equations (eqn ( 14) and ( 15)).were used to perform thermodynamic tting and research on the obtained data.The results can be seen from the gure.The corresponding thermodynamic parameter Gibbs freed the energy DG 0 , entropy change DS 0 , and enthalpy change DH 0 are shown in the table.
where DG 0 (kJ mol −1 ) is the Gibbs free energy, DS 0 (J mol −1 K −1 ) is the entropy change, and DH 0 (kJ mol −1 ) is the enthalpy change.It can be seen from Table S6 † that the positive enthalpy change (DH 0 , 11.184 kJ mol −1 ) indicates that MB adsorption on Fe 3 O 4 -N-BC is endothermic, and the positive entropy change (DS 0 , 44.623 J mol −1 K −1 ) indicates that the solid-liquid interface during the adsorption process disorder increases.The Gibbs free energy change of MB dropped from −2.1136 kJ mol −1 to −3.0061 kJ mol −1 within 298-318 K, which shows that this adsorption is a heat absorption process, and the adsorption of MB by Fe 3 O 4 -N-BC increases with the increase of temperature positive benecial effects.
Recyclability.Biochar loaded with Fe 3 O 4 can be easily separated from water under external force, has a high recovery rate, and is easy to reuse, which is a crucial feature in adsorbent applications.The regeneration potential of Fe 3 O 4 -N-BC is elucidated in Fig. 11.
In the desorption trial, 0.1 mol L −1 HCl solution served as the eluent to extract the adsorbed MB from the biomass charcoal.Aer ve adsorption-desorption times, the adsorption capacity of MB by Fe 3 O 4 -N-BC can still reach 497.18 mg g −1 , accounting for 80.36% of the rst adsorption capacity.The decrease in adsorption capacity with the number of cycles is due to the fact that MB on the surface of biomass charcoal permanently occupies some adsorption sites, resulting in some active sites being unavailable.Another reason is that part of the pore structure is blocked, resulting in fewer binding sites.The research results show that Fe 3 O 4 -N-BC has high stability and reusability, and has the potential to remove MB from wastewater.
Adsorption mechanism.Pore lling, electrostatic interaction, surface complex interaction, hydrogen bonding, pore diffusion, and p-p interaction are the mechanisms involved in MB adsorption by biomass carbon. 56,57Determining the adsorption mechanism is a challenging task because various factors oen inuence the adsorbent-adsorbate interaction simultaneously.The surface area, total pore volume, micropore volume, functional groups and hydrophilicity of biomass carbon will all affect its adsorption effect on MB.In order to study its adsorption mechanism, the adsorption of MB by biomass charcoal was analyzed and characterized.The specic surface area and pore volume of biomass charcoal hold pivotal signicance in the adsorption of MB.Activation with potassium hydroxide notably augments both its specic surface area and total pore volume, consequently heightening its efficacy in adsorbing MB.Moreover, the biomass charcoal has a higher adsorption capacity aer activation with potassium hydroxide.The carbon particles in material carbon can induce the formation of sp 3 disordered or defective carbon and sp 2 graphite during the activation process.The p-p bonds between the graphite lattice and methylene blue are improved due to the increased size and number of sp 3 disorder.Due to the high defect density, Fe 3 O 4 -N-BC has specic active sites for MB adsorption.Despite the anticipated pore structure diminution resulting from iron-nitrogen co-modication, it offers the advantage of introducing additional functional groups and  magnetic constituents.Various kinetic and equilibrium models were applied to the experimental dataset, revealing adherence to both the pseudo-second-order kinetic model and the Langmuir model.This suggests a signicant contribution of chemical adsorption in the MB adsorption process by Fe 3 O 4 -N-BC. 58n essence, the principal method of removing MB using Fe 3 O 4 -N-BC involves pore lling and p-p interaction, succeeded by hydrogen bonding and electrostatic interaction.The adsorption mechanism is depicted in Fig. 12.

Conclusions
In this study, N-modied banana peel biomass charcoal was generated by co-heating with urea at 700 °C and subsequently hydrothermal carbonization with Fe 3 O 4 at 180 °C, with the calcination temperature, calcination time, and amount of activator KOH.The Fe 3 O 4 -N-BC substance was produced in 4 hours.The resulting materials were characterized using a variety of analytical techniques.The synthesized magnetic biomass charcoal material has a high specic surface area and magnetic characteristics, as well as good MB adsorption capability.At 298 K, Fe 3 O 4 -N-BC has the greatest adsorption capacity of 638.08 mg g −1 MB at adsorption equilibrium.The pseudosecond-order kinetic model and the Langmuir isotherm model are both capable of accurately describing the adsorption kinetics and isotherm.The experimental data suggest that the adsorption of MB onto Fe 3 O 4 -N-BC is characterized by homogeneous monolayer adsorption rather than heterogeneous adsorption.Furthermore, the adsorption process is dominated by chemisorption.Remarkably, the adsorbent maintained a high MB adsorption capacity of 497.18 mg g −1 even aer ve regeneration cycles.This work creates an MB adsorbent by recycling waste biomass resources, which not only contributes to the sustainable development of natural resources, but also broadens the potential application scope of biomass waste and aids in the resolution of dye wastewater and resource use issues.
The strong adsorption performance of Fe 3 O 4 -N-BC on MB is predicted to be used for large-scale industrial wastewater treatment in the future.

Fig. 1
Fig.1The schematic representation of the synthesis of Fe 3 O 4 -N-BC.
) indicate that the synthesized Fe 3 O 4 particles exhibit a spherical shape with a rough surface.Clearly depicted in the gure is the spherical Fe 3 O 4 loaded onto the surface of biomass carbon.In order to understand the elemental composition of Fe 3 O 4 -N-BC material and the distribution of Fe 3 O 4 on BC, the EDS-mapping spectrum was used to analyse the Fe 3 O 4 -N-BC material.Fig. 4(b)-(f) are the element mappings of C, N, O, and Fe, respectively.The distribution of the four elements can be clearly shown in the gure.At the same time, the main distribution positions of O and Fe are roughly similar, which indicates that the synthesized Fe 3 O 4 was successfully loaded on the biomass charcoal.Fig. 5(a) shows the XRD patterns of BC, N-BC, Fe 3 O 4 , and Fe 3 O 4 -N-BC.According to the standard PDF card (JCPDF #75-0449), the values of 2q in the gure are at 18.4°(111), 30.3°(220), 35.7°(311), 37.4°(222), 43.4°(400), 53.9°(422), 57.5°(511), 63.1°(440), 71.6°(620), and 74.7°(533) are characteristic peaks of Fe 3 O 4 , which proves the presence of Fe 3 O 4 .Since amorphous carbon is prepared, its crystallinity is low, and broad peaks with low signal intensity appear near 28°and 40°.Because the diffraction peak intensity is weaker than that of Fe 3 O 4 , it is not obvious in the XRD pattern of Fe 3 O 4 -N-BC. 23The position of the characteristic peak of Fe 3 O 4 -N-BC is the same as that of Fe 3 O 4 , but the intensity of the peak is weakened.The XRD test results are related to the content of the sample.Compared with the pure Fe 3 O 4 sample, the relative Fe 3 O 4 content of Fe 3 O 4 -N-BC in the same amount of sample testing is reduced, so the XRD diffraction peak is relatively weakened.In Fig.5(b), the Raman spectrum of BC, N-BC, and Fe 3 O 4 -N-BC is presented.The D peak, observed around 1355 cm −1 , corresponds to the disorder or defects of carbon atoms, while the G peak, positioned near 1570 cm −1 , is associated with the surface stretching motion of sp 2 carbon atom pairs.30The two spectral bands of Fe 3 O 4 -N-BC illustrate the successful coating

Fig. 7
Fig. 7 (a) XPS survey spectra and (b) high-resolution XPS spectra of C 1s (c) high-resolution XPS spectra of O 1s of BC, N-BC and Fe 3 O 4 -N-BC, (d) high-resolution XPS spectra of Fe 2p of Fe 3 O 4 -N-BC.

Fig. 8
Fig. 8 (a) Adsorption capacity of MB by BC, N-BC and Fe 3 O 4 -N-BC, (b) effect of pH on MB adsorption.

Fig. 10 (
a) shows the effect of the initial dye concentration on the adsorption process of MB dye on Fe 3 O 4 -N-BC and the adsorption isotherm.At the test temperature, as the initial concentration increases, the adsorption amount of MB by Fe 3 O 4 -N-BC also increases until the adsorption equilibrium.The Langmuir (eqn (

k
L (L mg −1 ) is the Langmuir adsorption constant related to the adsorption capacity, k F (L g −1 ) is the Freundlich adsorption constant related to the adsorption capacity, n is the Freundlich constant indicating the difficulty of the reaction, R is the gas constant 8.314 (J mol −1 K −1 ), T (K) is the temperature, b (J mol −1 ) is the Temkin constant, A (L g −1 ) is an equilibrium constant related to binding energy.Analysis of the tted isotherm parameters (referenced in TableS5†) reveals that both the Temkin and Freundlich models inadequately describe the adsorption behavior of MB by Fe 3 O 4 -N-BC, as indicated by their comparatively low correlation coef-cients (R 2 ).Conversely, the Langmuir model boasts the highest correlation coefficient, nearing unity.This nding suggests that the adsorption mechanism of MB onto Fe 3 O 4 -N-BC predominantly adheres to the Langmuir adsorption isotherm.Consequently, it can be inferred that the adsorption behavior of MB on the Fe 3 O 4 -N-BC surface entails uniform monolayer adsorption, rather than heterogeneous adsorption.51The actual adsorption capacity of MB by Fe 3 O 4 -N-BC at 298 K is 638.08 mg g −1 .

Fig. 12
Fig. 12 Schematic diagram of the adsorption mechanism of methylene blue on biochar.

Table 1
Comparison of maximum MB removal capacity of various biochar Fig.11Regeneration performance.